An agricultural adjuvant

ABSTRACT

An agricultural adjuvant including at least one polyphenol containing natural or synthetic oil composition, the oil including blackcurrant (Ribes nigrum) seed oil. The agricultural adjuvant also includes at least one anionic surfactant, at least one nonionic surfactant, and at least one pH adjuster. The agricultural adjuvant may also include water and/or additives. The agricultural adjuvant may be provided as a stable concentrate form and a stable diluted form which is an emulsion Methods of manufacturing the agricultural adjuvant, uses thereof, and agricultural compositions including the agricultural adjuvant are also included.

FIELD OF DISCLOSURE

This disclosure relates to an agricultural adjuvant and use thereof, andextends to an agricultural composition.

BACKGROUND

Agricultural adjuvants are commonly used in agriculture to improveperformance and/or efficacy and/or delivery of one or more activeingredients which may be added to a tank mix of agrochemicals containingsaid active ingredient(s), or may be applied to soil or a cropindependently after application of said active ingredient(s). Typically,the active ingredient(s) may be chemically, biologically and/orphysiologically active, and may for example, be at least one of, but notlimited to, the following group: pesticides, insecticides, fungicides,herbicides, miticides, nematicides, plant growth regulators, defoliants,fertilizers and the like.

In cases where the active ingredient has a biochemical and/orphysiological function, it is desirous that the agricultural adjuvantprovides a more efficient delivery and/or provides a synergistic effectand/or is not on its own biochemically and/or physiologically activewhen applied to soil and/or plant matter, alternatively, that theagricultural adjuvant is not harmful to soil, seed, plant or crop. Thisis to avoid any biological and/or physiological side effects to thesoil, seed, plant or crop, and ultimately strives to ensure food safetyto end consumers. It is therefore desirous that agricultural adjuvantsthat improve performance and/or efficacy and/or delivery of one or moreactive ingredients, and not be an active ingredient in itself,alternatively, not to be harmful itself.

It is well known that certain adjuvants, surfactants, and otheradditives, are added to agrochemical compositions inside the same tankmix when in use. This reduces the water usage, limits compaction onsoil, and reduces time associated with irrigation, fertigation and/oradministration of plant protection products. However, adding adjuvantsand the like into an existing tank mix of an agrochemical compositionmay impact upon many physico-chemical properties of the agrochemicalcomposition, such as stability, solubility, volatility, dispersibility,viscosity, particle size, efficacy, freezing points and flash pointsthereof. This is important since any one or more physico-chemicalproperties may result in extra time, money, and water being spent onirrigation, fertigation, pest control, and application of plantprotection products, not to mention the negative effects of extracompaction of the soil by agricultural vehicles.

As such, some adjuvants may be highly effective to aid and facilitatebiological and/or physiological activity of active ingredients butconcomitantly may have negative impacts on physico-chemical propertiesof agrochemical compositions rendering their use ineffective. Further,certain adjuvants may improve certain physico-chemical properties of theagricultural composition but may concomitantly worsen otherphysico-chemical properties.

Often, chemical agents used to improve physico-chemical properties ofagrochemical compositions have negative impacts on biological and/orphysiological aspects of soil and/or plant matter.

Importantly, there is a major drive to provide agrochemical compositionsthat are environmentally friendly, safe to use on soil and plant matter,display low phytotoxicity, and are safe for end user handling.

WO 2006/052228 discloses an adjuvant for use with herbicides,pesticides, insecticides, ovicides and fungicides generally comprisingat least one surfactant and one high terpene (50% by weight or more).The surfactant assists with spreading the active ingredient when appliedto a soil or a crop therein preventing accumulation of active ingredientat one site. Accumulation of active ingredient increases concentrationthereof which often results in phytotoxicity which results in cropdamage. However, surfactants have a tendency to foam which results inaccumulation of active ingredient curbing spreading. In order to avoidfoaming and to encourage spreading so-called antifoaming agents areused. These are often silicon based and not acceptable for under organicfarming regulations in several jurisdictions, making them unsuitable foruse. Moreover, the high terpene displays a biological function as apesticide, insecticide, fungicide, miticide, ovicide and nematicide bycoating the aforementioned and smothering same. Concomitantly, the highterpene blocks stomata of leaves therein negatively impactingphotosynthesis and/or other physiological/biochemical functions. Thiscoating function is facilitated by a high surface tension. This isundesired since an adjuvant composition should not display biologicalactivity when applied to soil or plant matter, or should not be harmfulto the plant. All the examples disclose the high terpene to be coldpressed orange oil which is known to be both very flammable and to havea very low flashpoint of about 54° C. The flashpoint is generally knownas the lowest temperature at which a liquid can form an ignitablemixture in air near a surface of said liquid. The lower the flashpointthe easier the mixture and/or the surface can ignite. Moreover, thelower the flashpoint the higher the rate of evaporation which in turndecreases efficiency of agrochemical composition when in use. Lowflashpoints are not desired as it creates problems not only in use inhot and dry climates, but provides manufacturing and transportationrisks.

WO 2008/097553 disclosed a solution to the foaming problem describedabove by providing for a composition comprising a surfactant, a highterpene (50% by weight or more) being orange oil, a stabilizer, achelating agent, a preservative, an acid pH adjuster, and an organicsolvent. Although decreasing foaming and increasing spreading, the addedchemistries provide for increased environmental concerns and added coststo the manufacturing process. For example, the chelating agent disclosedis ethylenediaminetetraacetic acid (EDTA) which has a particularenvironmental and safety risk, and there has been a drive to discontinueits use owing to its potentially damaging effects on the environment.Further, the preservative disclosed includes propyl paraben and methylparaben which are known to negatively impact soil health conditions, aswell as negatively impact on photosynthesis in plants. Further, thesolvent disclosed is ethanol which is known to be a plant growthregulator (a ripening agent), therein displaying biochemical and/orphysiological activity in plant matter, and therefore not sought afteras being part of an agricultural adjuvant composition.

The physico-chemical impact of all the various added chemistries to thecompositions disclosed in the prior art, and the already disadvantageousbiological or physiological activity of the orange oil in soil and plantmaterial, leaves many disadvantages that require amelioration foragricultural adjuvants.

In agricultural adjuvant chemistry the resulting formulation is oftenprovided as an emulsion or a type of concentrate able to form anemulsion upon dilution. Stability of the concentrate and dilutedemulsion is important. The size of molecules within the concentrate anddiluted emulsion are also important. Often certain molecules within theconcentrate or diluted emulsion act as carrier molecules for activeingredients such as pesticides or even for fertilizing components. Thesize is important to ensure proper entry and uptake into plant tissue.

There is a need for new and innovative agricultural adjuvants which areeffective, and/or not biochemically and/or physiologically active ontheir own in soil or plant matter, and/or are environmentally friendly,and/or provide advantageous physico-chemical properties. There isfurther a general need to at least ameliorate the disadvantages known inthe prior art. This disclosure seeks to ameliorate the disadvantagesknown in the art.

SUMMARY

In accordance with a first aspect of this disclosure there is providedan agricultural adjuvant comprising:

at least one polyphenol containing natural or synthetic oil composition;

at least one anionic surfactant;

at least one nonionic surfactant; and

at least one pH adjuster.

The at least one polyphenol containing natural or synthetic oilcomposition may be a natural oil composition. The natural oilcomposition may be of vegetable origin. The natural oil of vegetableorigin may include at least one selected from, but not limited to, thegroup comprising, an essential oil, an edible oil, an oil extracted froma plant, an oil extracted from a part of a plant, an oil extracted froma tree, an oil extracted from a shrub, an oil extracted from a leaf, anoil extracted from a flower, an oil extracted from a grass, an oilextracted from a plant fluid, an oil extracted from an herb, an oilextracted from a fruit, an oil extracted from a seed, a mixture of oilsand combinations thereof.

The plant, or part of a plant, from which the natural oil of vegetableorigin is extracted may include at least one selected from, but notlimited to, the group comprising: angiosperms and/or gymnosperms.

The angiosperms may include at least one selected from, but not limitedto, the group comprising: oranges, apples, grapes, peaches, grapefruit,cherries, blueberries, pomegranate, raspberries, cranberries, blackelderberries, black currants, plums, blackberries, strawberries,apricots, spinach, onions, shallots, potatoes, olives, artichoke,broccoli, asparagus, carrots, cereals, wheat, rye, and oat, soybeans,black beans, white beans, chestnuts, hazelnuts, pecans, almonds,walnuts, flaxseed, coffee, tea, sesame, cocoa, capers, saffron, oregano,rosemary, cloves, peppermint, star anise, celery, sage, spearmint,thyme, basil, ginger, cumin, and cinnamon.

The gymnosperms may include at least one selected from, but not limitedto, the group comprising: conifers, cycads, ginko and gnetophytes.

The agricultural adjuvant wherein the at least one polyphenol containingnatural or synthetic oil composition may include at least one selectedfrom, but not limited to, the group comprising: flavonoids includinganthocyanins, chalcones, dihydrochalcones, flavanols, flavanones,flavones, flavonols, and isoflavanoids; lignans; stilbenes; and phenolicacids including hydroxybenzoic acid, hydroxycinnamic acid,hydroxyphenylacetic acid, hydroxyphenylpropanoic acid,hydroxyphenylpentanoic acid.

The agricultural adjuvant composition wherein the at least onepolyphenol containing natural or synthetic oil composition may includeat least one selected from, but not limited to, the group comprising:fatty acids including omega-3 fatty acid and omega-6 fatty acids;linoleic acid, terpenes, tocopherols, phytosterols, policosanols rangingfrom n-20:0-n-30:0 and 2-hydroxy fatty acids.

In a preferred embodiment of the disclosure the at least one polyphenolcontaining natural or synthetic oil composition includes black currant(Ribes nigrum) seed oil. The at least one polyphenol containing naturalor synthetic oil composition may be only black currant (Ribes nigrum)seed oil to the exclusion of others. The black currant (Ribes nigrum)seed oil may include polyphenols including, but not limited to,anthocyanins and flavonoids. The black currant (Ribes nigrum) seed oilmay include at least one of the following polyphenols:delphinidin-3-rutinoside, delphinidin-3-glucoside,cyanidin-3-rutinoside, cyanidin-3-glucoside, myricetin-3-rutinoside,myricetin-3-glucoside, quercetin-3-rutinoside, quercetin-3-glucoside,kaempferol-3-glucoside, dihydroquercetin, aureusidin,1-p-coumaroyl-β-d-glucopyranoside, 1-cinnamoyl-β-d-glucopyranoside,caffeic acid, ferulic acid, p-coumaric acid, gallic acid, protocatechuicacid and p-hydroxybenzoic acid.

In certain embodiments the at least one polyphenol containing natural orsynthetic oil composition further includes flavonoids belonging to oneof two classes: the anthocyanin class or the proanthocyanidin class, forexample, but not limited to: delphinidine-3-glucoside,delphinidine-3-rutinoside, cyanidine-3-glucoside, andcyanidine-3-rutinoside, high-molecular-weight galactans.

The at least one anionic surfactant may include at least one selectedfrom, but not limited to, the group comprising: (C₆-C₁₈) alkyl benzenesulfonic acid, calcium dodecylbenzene sulfonate, sodium dodecylbenzenesulfonate, amine (C₆-C₁₈) alkyl benzene sulfonate, triethanolaminedodecylbenzene sulfonates, (C₆-C₁₈) alkyl ether sulfates, (C₆-C₁₈) alkylethoxylated ether sulfates, (C₆-C₁₈) alkyl sulfates, lauryl etherpolyethoxylated sodium sulfate, (C₆-C₁₈) alkyl phosphate esters,(C₆-C₁₈) alkoxylated sulfates, (C₆-C₁₈) alkoxylated phosphate esters,xylene sulfonate salts, cumene sulfonate salts, lactic acid-basedanionic surfactants and combinations thereof.

In a preferred embodiment of the disclosure the at least one anionicsurfactant comprises dodecylbenzene sulfonic acid and/or sodium laurelether sulphate (SLES).

The at least one nonionic surfactant may include at least one selectedfrom, but not limited to, the group comprising: natural and/or synthetic(C₈-C₂₂) alkoxylated fatty alcohols, (C₈-C₂₂) ethoxylated fattyalcohols, (C₈-C₂₂) propoxylated fatty alcohols, (C₈-C₂₂) ethoxylated andpropoxylated fatty alcohols, straight chain (C₄-C₁₀)alkyl(poly)glycosides, branched chain (C₄-C₁₀) alkyl(poly)glycosides;and alkoxylated sorbitan fatty esters, alkoxylated sorbitol fattyesters, ethoxylated sorbitan fatty esters, ethoxylated sorbitol fattyesters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitanmonopalmitate, polyoxyethylene sorbitan monostearate, and combinationsthereof.

The ethoxylated fatty alcohols of fatty acids may have a degree ofethoxylation of from 1 to 50, more preferably 2 to 30, most preferably 3to 10.

Some alkoxylated alcohols contemplated for use include those based onbranched alcohols, such as the Guerbet alcohols, e.g. 2-propylheptanoland 2-ethylhexanol, and C₁₀-OXO-alcohol or C₁₃ OXO-alcohol, i.e. analcohol mixture whose main component is formed by at least one branchedC₁₀-alcohol or C₁₃-alcohol, and the alcohols commercially available asExxal alcohols from Exxon Mobile Chemicals and Neodol alcohols fromShell Chemicals.

In a preferred embodiment of the disclosure the non-ionic surfactantcomprises secondary alcohol (C₁₁-C₁₅) ethoxylates.

The pH adjuster may include a basic and/or an acid compound. The pHadjuster may include gluconic acid, barium carbonate, calcium chlorate,chlorous acid, sodium salt, sodium hydroxide, hydrobromic acid,tricalcium citrate.

In a preferred embodiment of this disclosure the pH adjuster may includesodium hydroxide and/or citric acid monohydrate. The pH adjuster allowsfor the adjuvant when in use to be stable across a wide range andprovides an adjuvant having a buffered pH of from about pH 4 to about pH8.

The agricultural adjuvant may further comprise a diluent, typicallywater.

The agricultural adjuvant may further comprise an additive and mayinclude at least one selected from, but not limited to, the groupcomprising: preservatives, clarifiers, anti-freezing agents,hydrotropes, stabilizers, antioxidants, acidifiers, chelates, complexingagents, dyes, rheology modifiers, antifoams, anti-drift and solvents,and combinations thereof.

The antioxidant may include at least one selected from, but not limitedto, the group comprising: butyl hydroxy toluene,3,5-bis(1,1-dimethylethyl)-4-hydroxy-, octadecyl ester, phenol,2,4-bis(1,1-dimethylethyl)-, 1,1′,1″-phosphite.

The stabilizer may include at least one selected from, but not limitedto, the group comprising: urea, polyvinyl alcohols, polyvinylpyrrolidone, methylcelluloses, hydroxyethyl- and propylcelluloses, andalso sodium carboxymethylcellulose, gelatin, casein, starch, gum arabic,hydroxy ethyl starch and sodium alginate.

The preservative may include at least one selected from, but not limitedto, the group comprising the following group: 2-phenoxy ethanol and1,2-benzisothiazolin-3-one.

The agricultural adjuvant of the first aspect of this disclosure mayfurther include at least one of, but not limited to, the followinggroup: insecticides, fungicides, herbicides, desiccants, defoliants,acaricides, nutrients, miticides, bactericides, biocides, ovicides,nematicides, insect growth regulators, plant growth regulators,fertilizers and combinations thereof.

The agricultural adjuvant of the first aspect of the invention mayfurther include an essential oil and may be kumquat (Citrus japonica)oil. Kumquat oil may comprise at least one of, but not limited to, thefollowing group: limonene (preferably d-limonene), alpha-pinene,bergamotene, caryophllene, α-humulene, α-muurolene, isopropylpropanoate, terpinyl acetate, carvone, citronellal, 2-methylundecanal,nerol and trans-linalool oxide.

The agricultural adjuvant of the first aspect of the disclosure may beformulated as a concentrate form (despite including a wt. % of waterdiluent). The concentrate form of the agricultural adjuvant of the firstaspect of the disclosure may be further diluted providing a diluted formprior to application and/or use on or to soil, seed, plant or crop. Thediluted form is typically present in a tank mix prior to application inuse.

In an example embodiment of the disclosure there is provided anagricultural adjuvant comprising:

-   -   at least one polyphenol containing natural or synthetic oil        composition present in an amount of between about 1 wt. % to        about 20 wt. % or any value therebetween;    -   at least one anionic surfactant present in an amount of between        about 2 wt. % to about 60 wt. % or any value therebetween;    -   at least one nonionic surfactant present in an amount of between        about 2 wt. % to about 20 wt. % or any value therebetween; and    -   at least one pH adjuster present in an amount of between about 1        wt. % to about 10 wt. % or any value therebetween, wherein the        wt. % is a total for the adjuvant.

The example embodiment of the disclosure may further comprise water as adiluent and/or other additives of about 2 wt. % to about 80 wt. % (orany value therebetween) of the water and/or other additives. Thisembodiment may still provide the liquid agricultural adjuvant inconcentrate form. All ranges presented in this disclosure include theminimum and the maximum presented in said range and includes any valuebetween the minimum and maximum.

In a further example embodiment of the disclosure there is provided anagricultural adjuvant comprising:

at least one polyphenol containing natural or synthetic oil compositionpresent in an amount of between about 1 wt. % to about 20 wt. %,preferably between about 2 wt. % and about 10 wt. %;

at least one anionic surfactant present in an amount of between about 2wt. % to about 60 wt. %, preferably between about 10 wt. % to about 50wt. %;

at least one nonionic surfactant present in an amount of between about 2wt. % to about 20 wt. %, preferably between about 5% wt. % and about 10wt. %; and

at least one pH adjuster present in an amount of between about 1 wt. %to about 10 wt. %, preferably between about 1 wt. % and about 5 wt. %,wherein the wt. % is a total for the adjuvant;

-   -   wherein the at least one polyphenol containing natural or        synthetic oil composition may be a natural oil composition of        vegetable origin selected from, but not limited to, the group        comprising: oranges, apples, grapes, peaches, grapefruit,        cherries, blueberries, pomegranate, raspberries, cranberries,        black elderberries, black currants, plums, blackberries,        strawberries, apricots, spinach, onions, shallots, potatoes,        olives, artichoke, broccoli, asparagus, carrots, cereals, wheat,        rye, and oat, soybeans, black beans, white beans, chestnuts,        hazelnuts, pecans, almonds, walnuts, flaxseed, coffee, tea,        sesame, cocoa, capers, saffron, oregano, rosemary, cloves,        peppermint, star anise, celery, sage, spearmint, thyme, basil,        ginger, cumin, cinnamon, conifers, cycads, ginko and        gnetophytes, preferably a natural oil composition of vegetable        origin from black currant (Ribes nigrum) seed oil    -   wherein the at least one anionic surfactant may be selected        from, but not limited to, the group comprising: (C₆-C₁₈) alkyl        benzene sulfonic acid salts, calcium dodecylbenzene sulfonate,        sodium dodecylbenzene sulfonate, amine (C₆-C₁₈) alkyl benzene        sulfonate, triethanolamine dodecylbenzene sulfonates, (C₆-C₁₈)        alkyl ether sulfates, (C₆-C₁₈) alkyl ethoxylated ether sulfates,        (C₆-C₁₈) alkyl sulfates, lauryl ether polyethoxylated sodium        sulfate, (C₆-C₁₈) alkyl phosphate esters, (C₆-C₁₈) alkoxylated        sulfates, (C₆-C₁₈) alkoxylated phosphate esters, xylene        sulfonate salts, cumene sulfonate salts, and combinations        thereof, preferably the at least one anionic surfactant        comprises dodecylbenzene sulfonic acid and/or sodium laurel        ether sulphate (SLES); and    -   wherein the at least one nonionic surfactant may be selected        from, but not limited to, the group comprising: (C₈-C₂₂)        alkoxylated fatty alcohols, (C₈-C₂₂) ethoxylated fatty alcohols,        (C₈-C₂₂) propoxylated fatty alcohols, (C₈-C₂₂) ethoxylated and        propoxylated fatty alcohols, straight chain (C₄-C₁₀)        alkyl(poly)glycosides, branched chain (C₄-C₁₀)        alkyl(poly)glycosides; and alkoxylated sorbitan fatty esters,        alkoxylated sorbitol fatty esters, ethoxylated sorbitan fatty        esters, ethoxylated sorbitol fatty esters, polyoxyethylene        sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,        polyoxyethylene sorbitan monostearate, and combinations thereof,        preferably the non-ionic surfactant comprises secondary alcohol        (C₁₁-C₁₅) ethoxylates; and    -   wherein the pH adjuster may include sodium hydroxide and/or        citric acid monohydrate.

The example embodiment of the disclosure may further comprise water as adiluent and/or other additives of about 2 wt. % to about 80 wt. % (orany value therebetween) of the water and/or other additives. Thisembodiment may still provide the liquid agricultural adjuvant inconcentrate form.

The example embodiment of the disclosure may further comprise kumquat(Citrus japonica) oil. The kumquat (Citrus japonica) oil may comprisebetween about 0.05 wt. % to about 5 wt. %, preferably between about 0.5wt. % to about 3 wt. %, further preferably between about 0.8 wt. % toabout 2 wt. %.

The agricultural adjuvant may be formulated and/or adapted to provide aspray composition for application to soil and/or plants in agriculture.

The Applicant has surprisingly found that the agricultural adjuvantaccording to the first aspect of this disclosure provides for aphysico-chemically stable and homogenous concentrate form which, whendiluted, provides a stable diluted emulsion or micro-emulsion or nanoemulsions. The agricultural adjuvant displays a flashpoint of greaterthan about 100° C. providing a safe adjuvant in both concentrate anddilute forms. Surprisingly the agricultural adjuvant shows littlefoaming in use, and better spreading, wetting and penetrationcharacteristics in use compared to a commercially available equivalent.Without being limited to theory, the Applicant submits that it is theunique combination of essential features comprising the agriculturaladjuvant that assists in ameliorating the disadvantages of the priorart. Further the claimed wt. % of the various different essentialfeatures as a portion of the total wt. % of the agricultural adjuvantmay further facilitate imparting the advantages shown here below.

A skilled person in the art would not have considered an agriculturaladjuvant including at least one polyphenol containing natural orsynthetic oil composition since prior art natural oils provide for lowflashpoints and have been shown to be harmful to plants and/orbiochemically or physiologically active. Without being limited totheory, the Applicant believes that the unique chemical composition ofthe at least one polyphenol containing natural or synthetic oilcomposition provides means to overcome the disadvantages seen in theprior art. Further, the unique chemical composition of the at least onepolyphenol containing natural or synthetic oil composition together withthe remaining essential elements further assists in overcoming the priorart disadvantages.

The Applicant has surprisingly found that the agricultural adjuvantaccording to the first aspect of the disclosure protects activeingredients from damage by ultraviolet (UV) radiation. This facilitatesproviding plant and/or soil material with a greater quantity of activeingredient in regions that might experience or receive above average UVradiation. This further facilitates using less active ingredient toachieve a similar or same result.

The Applicant has surprisingly found that the agricultural adjuvantaccording to the first disclosure is more effective when compared tocommercial prior art adjuvant. Increasing efficacy allows less activeingredient to be utilized whilst not compromising end results, and inturn, hinders biological resistance to active ingredients. Hinderingand/or preventing resistance of active ingredients including at leastone of pesticides, insecticides, fungicides, herbicides, miticides,nematicides, plant growth regulators, defoliants, fertilizers, istremendously advantageous in commercial farming operations.

The Applicant has also surprisingly and unexpected found that apreferred embodiment of the disclosure provides uniquely smaller sizedmolecules within a resulting concentrated or diluted form, bothtypically providing a stable emulsion.

In accordance with a second aspect of this disclosure there is provideda method for manufacturing an agricultural adjuvant as described in thefirst aspect of this disclosure, the method comprising the followingsteps:

-   -   (i). adding at least one polyphenol containing natural or        synthetic oil composition into a mixing vessel;    -   (ii). adding at least one anionic surfactant to the mixing        vessel;    -   (iii). adding at least one nonionic surfactant to the mixing        vessel; and    -   (iv). adding at least one pH adjuster to the mixing vessel,        -   wherein steps (i) to (iv) conducted in any order provides            for the concentrate form of the agricultural adjuvant.

The at least one polyphenol containing natural or synthetic oilcomposition, the at least one anionic surfactant, the at least onenonionic surfactant, and the at least one pH adjuster may as describedin the first aspect of this disclosure above.

The method may further include the step of introducing a diluent,typically water.

The method may further include the step of introducing an additive andmay include at least one selected from, but not limited to, the groupcomprising: preservatives, clarifiers, anti-freezing agents,hydrotropes, stabilizers, antioxidants, acidifiers, chelates, complexingagents, dyes, rheology modifiers, antifoams, anti-drift and solvents,and combinations thereof.

The method may further include the step of introducing at least one of,but not limited to, the following group: insecticides, fungicides,herbicides, desiccants, defoliants, acaricides, nutrients, miticides,bactericides, biocides, ovicides, nematicides, insect growth regulators,plant growth regulators, fertilizers and combinations thereof.Preferably, this step provides for a spray composition for applicationto plants and/or soil in agriculture. The method may further include anyother component disclosed in the first aspect of the disclosure above.

The method according to this second aspect of the disclosure provides aconcentrate form (despite including a wt. % of water diluent). Theconcentrate form of the agricultural adjuvant of the first aspect of thedisclosure may be further diluted prior to application and/or use on orto soil, seed, plant or crop.

In accordance with a third aspect of this disclosure there is provided amethod of diluting the agricultural adjuvant described in the firstaspect of this disclosure, the method comprising:

-   -   diluting the adjuvant concentrate prepared according as        described in the first aspect of the disclosure above with water        at a ratio by weight of liquid agricultural adjuvant to water        1:5000 to 1:10 to yield a stable diluted emulsion and/or        microemulsion and/or nano emulsion. It is to be understood that        the water may further contain at least one agricultural compound        selected from, but not limited to, the group comprising:        insecticides, fungicides, herbicides, desiccants, defoliants,        acaricides, nutrients, miticides, bactericides, biocides,        ovicides, nematicides, insect growth regulators, plant growth        regulators, and combinations thereof.

The method wherein the liquid agricultural adjuvant may be diluted in aat least one of, but not limited to, the following group: a mixing tank,a spray tank, a container, or an inline irrigation system, thereinproviding the diluted liquid agricultural adjuvant which may be a stablediluted emulsion or microemulsion or nano emulsions that facilitatesrain-fastness through accelerated uptake into the plant owing to forexample wax dissolution capability of the adjuvant.

The method wherein the stable diluted emulsion and/or microemulsionand/or nano emulsions may be applied on at least one member of, but notlimited to, the group comprising: plants, weeds, seeds, soil, urbanplaces, and forests, via an apparatus selected from, but not limited to,the group comprising: air assisted sprayers, conventional sprayers,ultra-low volumes equipment such as aerial, electrostatic, foggers andmisting spray equipment and chemigation systems, pivots, sprinklers, andcombinations thereof. The disclosure extends to uses of the agriculturaladjuvant.

In accordance with a fourth aspect of this disclosure there is provideduse of the agricultural adjuvant described in the first aspect of thisdisclosure in agriculture, said use comprising the steps of:

(i) combining the agricultural adjuvant of the first aspect togetherwith water to provide a dilute form and at least one agriculturalcompound selected from, but not limited to, the group comprising:insecticides, fungicides, herbicides, desiccants, defoliants,acaricides, nutrients, miticides, bactericides, biocides, ovicides,nematicides, insect growth regulators, plant growth regulators, andcombinations thereof, to provide a mixture; and

(ii) applying the mixture to plants, weeds, seeds, soil, urban places,and forests, via an apparatus selected from, but not limited to, thegroup comprising: air assisted sprayers, conventional sprayers,ultra-low volumes equipment such as aerial, electrostatic, foggers andmisting spray equipment and chemigation systems, pivots, sprinklers, andcombinations thereof.

In accordance with a fifth aspect of this disclosure there is providedan agricultural composition comprising:

at least one polyphenol containing natural or synthetic oil composition;

at least one anionic surfactant;

at least one nonionic surfactant; and

at least one pH adjuster.

The at least one polyphenol containing natural or synthetic oilcomposition may be as described in the first to third aspects of thedisclosure above.

The at least one anionic surfactant may be as described in the first tothird aspects of the disclosure above.

The at least one nonionic surfactant may be as described in the first tothird aspects of the disclosure above.

The at least one nonionic surfactant may be as described in the first tothird aspects of the disclosure above.

The at least one pH adjuster may be as described in the first to thirdaspects of the disclosure above. The at least one nonionic surfactantmay be as described in the first to third aspects of the disclosureabove.

The agricultural composition of the fifth aspect of this disclosure mayfurther include at least one of, but not limited to, the followinggroup: insecticides, fungicides, herbicides, desiccants, defoliants,acaricides, nutrients, miticides, bactericides, biocides, ovicides,nematicides, insect growth regulators, plant growth regulators,fertilizers and combinations thereof.

The agricultural adjuvant of the fifth aspect of the invention mayfurther include an essential oil and may be kumquat (Citrus japonica)oil. Kumquat oil may comprise at least one of, but not limited to, thefollowing group: limonene (preferably d-limonene), alpha-pinene,bergamotene, caryophllene, α-humulene, α-muurolene, isopropylpropanoate, terpinyl acetate, carvone, citronellal, 2-methylundecanal,nerol and trans-linalool oxide.

The agricultural composition according to the fifth aspect of theinvention may be formulated with additional chemistries and/or adiluent. The agricultural composition may provide a tank mix partnerproviding in use a stable tank mix. The agricultural composition mayprovide an in-can formulation partner providing in use a stable in-canformulation. Stability is an important property to ensure effective useand/or application of the agricultural formulation to plant, soil and/orseed material.

The agricultural composition according to the fifth aspect of theinvention may be formulated and/or provided as a pesticide.

The agricultural composition may be provided as a tank mix and/or as anin-can formulation. Tank mixes may include multicomponentchemical-compositions mixed inside a tank from which irrigation and/orfertigation will take place. In-can formulations include multicomponentchemical-compositions within a single can (or container), whereinindividual components may have different chemical properties when in useand wherein the single can (or container) may be sold as a stand aloneitem including therein the different multi-components.

The Applicant believes that the subject matter of the disclosuredescribed herein at least ameliorates one of the disadvantages known inthe current state of the art.

While the subject matter of the disclosure has been described in detailwith respect to specific embodiments and/or examples thereof, it will beappreciated that those skilled in the art, upon attaining anunderstanding of the foregoing may readily conceive of alterations to,variations of and equivalents to these embodiments. Accordingly, thescope of the present disclosure should be assessed as that of the claimsand any equivalents thereto, which claims are appended hereto.

BRIEF DESCRIPTION OF THE FIGURES

Embodiments of the disclosure will be described below by way of exampleonly and with reference to the accompanying drawings in which:

FIG. 1 shows a time-dependent sessile contact angle development on theadaxial side of wheat during the first 60 seconds after dropletapplication for WETCIT® 0.1% and ORO-368 0.1 and 0.05% in water (w/v).Water was used as a control. Symbols represent mean values and errorbars illustrate the standard deviation, n≥10.

FIG. 2 shows a time-dependent sessile contact angle development on theabaxial side of wheat during the first 60 seconds after dropletapplication for WETCIT® 0.1% and ORO-368 0.1% and 0.05% in water (w/v).Water was used as a control. Symbols represent mean values and errorbars illustrate the standard deviation, n≥10.

FIG. 3 shows results from a covered leaf area in mm² of 3 μL volumesurfactant droplets. Comparison between adaxial (black) and abaxial side(grey) of Triticum aestivum leaves. Water was used as a control. Barsrepresent mean values and error bars illustrate the standard deviation,n≥10, paired samples from contact angle experiments.

FIG. 4 shows a comparison of freshly settled droplets (3 μl volume) anddroplet residue after water evaporation of the surfactant solutions onadaxial Triticum aestivum leaves.

FIG. 5 shows a dominant surface structures of parafilm are absent(higher magnification (A), lower magnification (B)).

FIG. 6 shows a comparison of surface microstructures of the adaxial(left) and the abaxial (right) side of Triticum aestivum. Magnificationincreases from top to bottom. Non-glandular trichomes were orientated inparallel on both sides of the leaf (A and B). Surface structures onthese trichomes reveal no wax crystals in a higher magnification (C andD). Epicuticular wax crystals are also present on both leaf sides (E andF).

FIG. 7 shows droplet residues of WETCIT® 0.1% (A and B) and ORO-368 0.1%(C and D) solutions in water (w/v) on Triticum aestivum leaves.Magnification increases from left to right.

FIG. 8 shows spreading properties of the adjuvant according to thisdisclosure ORO 368 compared to known adjuvants such as COC, MSO and NIS.

FIG. 9 shows efficacy and crop selectivity of ORO 368 were conducted ina tank mix against Septoria tritici in wheat.

FIG. 10 shows efficacy trials with an herbicide in maize and unwantedplants/weeds.

FIG. 11 shows efficacy trials with an herbicide in maize and unwantedplants/weeds.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE DISCLOSURE

The content of the Summary above is fully repeated herein by way ofreference and to avoid unnecessary repetition. However, non-limitingaspects of the disclosure are provided here to include an agriculturaladjuvant and/or agricultural composition, a method for manufacturing theaforementioned, and its use are described herein.

Providing safe and effective adjuvants having low flashpoints,exhibiting stability in a concentrate and dilute form, not being harmfulto soil, seed, or plant matter (or additionally and/or alternatively notbeing biochemically and/or physiologically active) remains a challengingendeavor. Further, providing adjuvants that in use are effectivelyretained onto plant matter and provide in use effective spreading and/orwetting and/or penetration characteristics remains a challengingendeavor. Slight variations to adjuvant formulations may have majordisadvantageous impacts on the physico-chemical properties thereof andmay make same wholly unsuitable for use in agriculture. Further,providing agricultural adjuvants that provide molecules with particlesizes that are small enough to ensure efficient uptake into and througha plant whilst is another challenge.

Typically, agricultural adjuvants are tank mixed and sprayed onto aplant surface. High efficiency spray retention of the adjuvant onto theplant surface is required for maximizing delivery of active ingredientsin agrochemicals including active ingredients present in insecticides,fungicides, herbicides, desiccants, defoliants, acaricides, nutrients,miticides, bactericides, biocides, ovicides, nematicides, insect growthregulators, plant growth regulators, fertilizers and/or crop protectionagrochemicals and combinations thereof.

Increasing the retention of adjuvant on a plant/seed/soil surfaceincreases the amount of active ingredient potentially available forreaching a biological site of action. Retention may be understood as theoverall capture of spray droplets by a plant and determines the amountof active ingredient on a plant and therefore possibly available to theplant. Retention is dependent on a complex interfacial interaction ofadjuvant spray droplets and the plant surface itself. Factors consideredto be important for adjuvant spray liquid adhesion and retentioninclude: (i) physico-chemical properties of the agricultural adjuvantconcentrate form and therefore also its diluted form sprayed as asolution from a tank mix; (ii) diameter spectra and impaction velocityof adjuvant spray droplets; and (iii) characteristics of plant surface,shape and orientation of the target leaves and density of plant canopy.

For plants, wettability of the leaf surface is typically governed bysurface roughness caused by different microstructures (for exampletrichomes, cuticular folds and wax crystals), together with thehydrophobic properties of the epicuticular wax. Hydrophobicity ofepicuticular wax and the microstructures can efficiently reduce thedeposition and retention of adjuvant spray droplets by increasingcontact angles and reducing contact area with plant leaf surface.

The physico-chemical properties, which are complex, of the adjuvant isthe most important factor determining the outcome of the interactionbetween plant surface and spray solutions. Consequently, the differentchemical components and their interactions together as part of anagricultural adjuvant are important considerations. Predictingphysico-chemical properties of an agricultural adjuvant from its variouschemical components is not readily possible. Further, predictingphysiological and/or biochemical interactions is a near impossibility.

There is a need for new and innovative agricultural adjuvants which areeffective, not biochemically and/or physiologically active on their ownin soil or plant matter (or are not harmful to plants), areenvironmentally friendly, and provide advantageous physico-chemicalproperties. There is further a general need to at least ameliorate thedisadvantages known in the prior art.

To at least ameliorate the disadvantage of the prior art, and inaccordance with a first aspect of this disclosure there is provided anagricultural adjuvant.

The agricultural adjuvant comprises at least one polyphenol containingnatural or synthetic oil composition, at least one anionic surfactant,at least one nonionic surfactant, and at least one pH adjuster. Withoutbeing limited to theory, the Applicant believes that the unique chemicalcomposition of the at least one polyphenol containing natural orsynthetic oil composition provides means to overcome the disadvantagesseen in the prior art. Further, the unique chemical composition of theat least one polyphenol containing natural or synthetic oil compositiontogether with the remaining essential elements further assists inovercoming the prior art disadvantages.

The at least one polyphenol containing natural or synthetic oilcomposition may be a natural oil composition, preferably the natural oilcomposition may be of vegetable origin. The natural oil of vegetableorigin may include at least one selected from, but not limited to, thegroup comprising, an essential oil, an edible oil, an oil extracted froma plant, an oil extracted from a part of a plant, an oil extracted froma tree, an oil extracted from a shrub, an oil extracted from a leaf, anoil extracted from a flower, an oil extracted from a grass, an oilextracted from a plant fluid, an oil extracted from an herb, an oilextracted from a fruit, an oil extracted from a seed, a mixture of oilsand combinations thereof.

The plant, or part of a plant, from which the natural oil of vegetableorigin is extracted may include at least one selected from, but notlimited to, the group comprising: angiosperms and/or gymnosperms. Theangiosperms may include at least one selected from, but not limited to,the group comprising: oranges, apples, grapes, peaches, grapefruit,cherries, blueberries, pomegranate, raspberries, cranberries, blackelderberries, black currants, plums, blackberries, strawberries,apricots, spinach, onions, shallots, potatoes, olives, artichoke,broccoli, asparagus, carrots, cereals, wheat, rye, and oat, soybeans,black beans, white beans, chestnuts, hazelnuts, pecans, almonds,walnuts, flaxseed, coffee, tea, sesame, cocoa, capers, saffron, oregano,rosemary, cloves, peppermint, star anise, celery, sage, spearmint,thyme, basil, ginger, cumin, and cinnamon. The gymnosperms may includeat least one selected from, but not limited to, the group comprising:conifers, cycads, ginko and gnetophytes.

The agricultural adjuvant wherein the at least one polyphenol containingnatural or synthetic oil composition may include at least one selectedfrom, but not limited to, the group comprising: flavonoids includinganthocyanins, chalcones, dihydrochalcones, flavanols, flavanones,flavones, flavonols, and isoflavanoids; lignans; stilbenes; and phenolicacids including hydroxybenzoic acid, hydroxycinnamic acid,hydroxyphenylacetic acid, hydroxyphenylpropanoic acid,hydroxyphenylpentanoic acid.

The agricultural adjuvant composition wherein the at least onepolyphenol containing natural or synthetic oil composition may includeat least one selected from, but not limited to, the group comprising:fatty acids including omega-3 fatty acid and omega-6 fatty acids;linoleic acid, terpenes, tocopherols, phytosterols, policosanols rangingfrom n-20:0-n-30:0 and 2-hydroxy fatty acids.

In a preferred embodiment of the disclosure the at least one polyphenolcontaining natural or synthetic oil composition includes black currant(Ribes nigrum) seed oil, and/or may include black currant (Ribes nigrum)seed oil to the exclusion of others. The black currant (Ribes nigrum)seed oil may include polyphenols including, but not limited to,anthocyanins and flavonoids. The black currant (Ribes nigrum) seed oilmay include at least one of the following polyphenols:delphinidin-3-rutinoside, delphinidin glucoside, cyanidin-3-rutinoside,cyanidin-3-glucoside, myricetin-3-rutinoside, myricetin-3-glucoside,quercetin-3-rutinoside, quercetin-3-glucoside, kaempferol-3-glucoside,dihydroquercetin, aureusidin, 1-p-coumaroyl-β-d-glucopyranoside,1-cinnamoyl-β-d-glucopyranoside, caffeic acid, ferulic acid, p-coumaricacid, gallic acid, protocatechuic acid and p-hydroxybenzoic acid.

In certain embodiments the at least one polyphenol containing natural orsynthetic oil composition includes flavonoids belong to one of twoclasses: the anthocyanin class or the proanthocyanidin class, forexample, but not limited to: delphinidine-3-glucoside,delphinidine-3-rutinoside, cyanidine-3-glucoside, andcyanidine-3-rutinoside, high-molecular-weight galactans.

The at least one anionic surfactant may include at least one selectedfrom, but not limited to, the group comprising: (C₆-C₁₈) alkyl benzenesulfonic acid, calcium dodecylbenzene sulfonate, sodium dodecylbenzenesulfonate, amine (C₆-C₁₈) alkyl benzene sulfonate, triethanolaminedodecylbenzene sulfonates, (C₆-C₁₈) alkyl ether sulfates, (C₆-C₁₈) alkylethoxylated ether sulfates, (C₆-C₁₈) alkyl sulfates, lauryl etherpolyethoxylated sodium sulfate, (C₆-C₁₈) alkyl phosphate esters,(C₆-C₁₈) alkoxylated sulfates, (C₆-C₁₈) alkoxylated phosphate esters,xylene sulfonate salts, cumene sulfonate salts, and combinationsthereof. In a preferred embodiment of the disclosure the at least oneanionic surfactant comprises dodecylbenzene sulfonic acid and/or sodiumlaurel ether sulphate (SLES).

The at least one nonionic surfactant may include at least one selectedfrom, but not limited to, the group comprising: natural and/or synthetic(C₈-C₂₂) alkoxylated fatty alcohols, (C₈-C₂₂) ethoxylated fattyalcohols, (C₈-C₂₂) propoxylated fatty alcohols, (C₈-C₂₂) ethoxylated andpropoxylated fatty alcohols, straight chain (C₄-C₁₀)alkyl(poly)glycosides, branched chain (C₄-C₁₀) alkyl(poly)glycosides;and alkoxylated sorbitan fatty esters, alkoxylated sorbitol fattyesters, ethoxylated sorbitan fatty esters, ethoxylated sorbitol fattyesters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitanmonopalmitate, polyoxyethylene sorbitan monostearate, and combinationsthereof. In a preferred embodiment of the disclosure the non-ionicsurfactant comprises secondary alcohol (C₁₁-C₁₅) ethoxylates.

The pH adjuster may include a basic and/or an acid compound. In apreferred embodiment of this disclosure the pH adjuster may includesodium hydroxide and/or citric acid monohydrate. The pH adjusterprovides for an agricultural adjuvant which does not precipitate out ofsolution in its concentrate form, and provides for a pH buffered rangewhen the adjuvant is diluted in a tank mix prior to application.Different soils and/or plants require a different pH for optimaldelivery of an active ingredient. Further different active ingredientsrequire different pH values for effective delivery or to preventunwanted chemical side reactions which would render the activeingredient useful. Providing a pH buffered range between about pH 4 andabout pH 8 from a single adjuvant allows great flexibility in use. Thebuffered pH range also allows the agricultural adjuvant to be compatiblewith a host of different agrochemicals when in use.

The agricultural adjuvant may further comprise a diluent, typicallywater. The agricultural adjuvant may further comprise an additive andmay include at least one selected from, but not limited to, the groupcomprising: preservatives, clarifiers, anti-freezing agents,hydrotropes, stabilizers, antioxidants, acidifiers, chelates, complexingagents, dyes, rheology modifiers, antifoams, anti-drift and solvents,and combinations thereof. The example embodiment of the disclosure mayfurther comprise water as a diluent and/or other additives of about 2wt. % to about 80 wt. % (or any value therebetween) of the water and/orother additives. This embodiment may still provide the liquidagricultural adjuvant in concentrate form. All ranges presented in thisdisclosure include the minimum and the maximum presented in said rangeand includes any value between the minimum and maximum.

The anti-oxidant is typically butyl hydroxy toluene. The stabilizer istypically urea. The preservative is typically 2-phenoxy ethanol and1,2-benzisothiazolin-3-one.

The agricultural adjuvant of the first aspect of this disclosure mayfurther include at least one of, but not limited to, the followinggroup: insecticides, fungicides, herbicides, desiccants, defoliants,acaricides, nutrients, miticides, bactericides, biocides, ovicides,nematicides, insect growth regulators, plant growth regulators,fertilizers and combinations thereof.

The agricultural adjuvant of the fifth aspect of the invention mayfurther include an essential oil and may be kumquat (Citrus japonica)oil. Kumquat oil may comprise at least one of, but not limited to, thefollowing group: limonene (preferably d-limonene), alpha-pinene,bergamotene, caryophllene, α-humulene, α-muurolene, isopropylpropanoate, terpinyl acetate, carvone, citronellal, 2-methylundecanal,nerol and trans-linalool oxide.

The agricultural adjuvant of the first aspect of the disclosure may beformulated as a concentrate form (despite including a wt. % of waterdiluent). The concentrate form of the agricultural adjuvant of the firstaspect of the disclosure may be further diluted prior to applicationand/or use on or to soil, seed, plant or crop. Both the concentrate formand diluted form may provide a stable emulsion.

In a further example embodiment of the disclosure there is provided anagricultural adjuvant comprising:

at least one polyphenol containing natural or synthetic oil compositionpresent in an amount of between about 1 wt. % to about 20 wt. %,preferably between about 2 wt. % and about 10 wt. %, further preferablybetween about 5 wt. % and about 8 wt. %;

at least one anionic surfactant present in an amount of between about 2wt. % to about 60 wt. %, preferably between about 10 wt. % to about 50wt. %, further preferably between about 20 wt. % and about 30 wt. %;

at least one nonionic surfactant present in an amount of between about 2wt. % to about 20 wt. %, preferably between about 5 wt. % and about 10wt. %, further preferably between about 7 wt. % and about 8 wt. %; and

at least one pH adjuster present in an amount of between about 1 wt. %to about 10 wt. %, preferably between about 1 wt. % and about 5 wt. %,further preferably between about 1 wt. % and about 2 wt. %;

wherein the wt. % is a total for the adjuvant; and

-   -   wherein the at least one polyphenol containing natural or        synthetic oil composition may be a natural oil composition of        vegetable origin selected from, but not limited to, the group        comprising: oranges, apples, grapes, peaches, grapefruit,        cherries, blueberries, pomegranate, raspberries, cranberries,        black elderberries, black currants, plums, blackberries,        strawberries, apricots, spinach, onions, shallots, potatoes,        olives, artichoke, broccoli, asparagus, carrots, cereals, wheat,        rye, and oat, soybeans, black beans, white beans, chestnuts,        hazelnuts, pecans, almonds, walnuts, flaxseed, coffee, tea,        sesame, cocoa, capers, saffron, oregano, rosemary, cloves,        peppermint, star anise, celery, sage, spearmint, thyme, basil,        ginger, cumin, cinnamon, conifers, cycads, ginko and        gnetophytes, preferably black currant (Ribes nigrum) seed oil;    -   wherein the at least one anionic surfactant may be selected        from, but not limited to, the group comprising: (C₆-C₁₈) alkyl        benzene sulfonic acid salts, calcium dodecylbenzene sulfonate,        sodium dodecylbenzene sulfonate, amine (C₆-C₁₈) alkyl benzene        sulfonate, triethanolamine dodecylbenzene sulfonates, (C₆-C₁₈)        alkyl ether sulfates, (C₆-C₁₈) alkyl ethoxylated ether sulfates,        (C₆-C₁₈) alkyl sulfates, lauryl ether polyethoxylated sodium        sulfate, (C₆-C₁₈) alkyl phosphate esters, (C₆-C₁₈) alkoxylated        sulfates, (C₆-C₁₈) alkoxylated phosphate esters, xylene        sulfonate salts, cumene sulfonate salts, and combinations        thereof, preferably the at least one anionic surfactant        comprises dodecylbenzene sulfonic acid and/or sodium laurel        ether sulphate (SLES); and    -   wherein the at least one nonionic surfactant may be selected        from, but not limited to, the group comprising: (C₈-C₂₂)        alkoxylated fatty alcohols, (C₈-C₂₂) ethoxylated fatty alcohols,        (C₈-C₂₂) propoxylated fatty alcohols, (C₈-C₂₂) ethoxylated and        propoxylated fatty alcohols, straight chain (C₄-C₁₀)        alkyl(poly)glycosides, branched chain (C₄-C₁₀)        alkyl(poly)glycosides; and alkoxylated sorbitan fatty esters,        alkoxylated sorbitol fatty esters, ethoxylated sorbitan fatty        esters, ethoxylated sorbitol fatty esters, polyoxyethylene        sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,        polyoxyethylene sorbitan monostearate, and combinations thereof,        preferably the non-ionic surfactant comprises secondary alcohol        (C₁₁-C₁₅) ethoxylates; and    -   wherein the pH adjuster may include sodium hydroxide and/or        citric acid monohydrate.

The example embodiment of the disclosure may further comprise water as adiluent and/or other additives of about 2 wt. % to about 80 wt. % (orany value therebetween) of the water and/or other additives. Thisembodiment may still provide the liquid agricultural adjuvant inconcentrate form.

In a further example embodiment the disclosure may further comprisekumquat (Citrus japonica) oil. The kumquat (Citrus japonica) oil maycomprise between about 0.05 wt. % to about 5 wt. %, preferably betweenabout 0.5 wt. % to about 3 wt. %, further preferably between about 0.8wt. % to about 2 wt. %.

The Applicant has surprisingly found that the agricultural adjuvantaccording to the first aspect of the disclosure protects activeingredients from damage by ultraviolet (UV) radiation. This facilitatesproviding plant and/or soil material with a greater quantity of activeingredient in regions that might experience or receive above average UVradiation. This further facilitates using less active ingredient toachieve a similar or same result.

The Applicant has surprisingly found that the agricultural adjuvantaccording to the first disclosure is more effective when compared tocommercial prior art adjuvant. Increasing efficacy allows less activeingredient to be utilized in a tank mix whilst not compromising endresults, and in turn, hinders biological resistance to activeingredients. Hindering and/or preventing resistance of activeingredients including at least one of pesticides, insecticides,fungicides, herbicides, miticides, nematicides, plant growth regulators,defoliants, fertilizers, is tremendously advantageous in commercialfarming operations.

In accordance with a second aspect of this disclosure there is provideda method for manufacturing an agricultural adjuvant as described in thefirst aspect of this disclosure, the method comprising the followingsteps:

-   -   (i). adding at least one polyphenol containing natural or        synthetic oil composition into a mixing vessel;    -   (ii). adding at least one anionic surfactant to the mixing        vessel;    -   (iii). adding at least one nonionic surfactant to the mixing        vessel; and    -   (iv). adding at least one pH adjuster to the mixing vessel,        -   wherein steps (i) to (iv) conducted in any order provides            for the concentrate form of the agricultural adjuvant. It is            to be understood that the sequence of steps (i) to (iv) may            vary. The method for manufacturing the agricultural adjuvant            is simple and scalable. Upscaling is often complicated by            individual chemical components of an agricultural adjuvant.            Arriving at a particular agricultural adjuvant that not only            effectively functions as an adjuvant whilst not harming            plants, but is also can be upscaled for commercial            production is a major advantage. Adding to this advantage is            the high (greater than about 100° C.) flashpoint of the            agricultural adjuvant of the first aspect. Prior art            adjuvants having natural or essential oils have previously            been found to have low flashpoints making the manufacture,            handling and use dangerous. A higher flashpoint makes the            commercial manufacture significantly safer. A higher            flashpoint further provides for less evaporation of active            ingredient providing an increased period of time for the            active ingredient to reach its intended target in the plant            and/or soil.

The agricultural adjuvant of the present disclosure is made by combiningand mixing the components of such composition described in the firstaspect herein.

In a 1000 ml glass reactor equipped with a cooling system, 200.0 g ofwater and an amount between 60 to 85 g of dodecylbenzene sulphonic acidwere mixed and then an amount of sodium hydroxide was added until the pHreaches neutrality. The reactor was then maintained at the roomtemperature for 1 h until the reaction mixture was cooled down. Anamount 70 to 200 grams of sodium laurel ether sulphate and 50 to 100 gof a secondary alcohol ethoxylate were added to the vessel. Finally, 30to 70 grams of a natural or synthetic oil such as black currant solidwas added and heated to 50° C. The solution was then stabilized byadding 5 to 15 grams of urea, cooled down and an antioxidant such as thebutyl hydroxy toluene and a preservative such as 2-phenoxy ethanol wereadded to the mixture.

Physico-chemical analyses were conducted on the agricultural adjuvant ofthis disclosure, with the following results:

Concentrate form of the agricultural adjuvant pH (value) 7-8 (at 20° C.)

Diluted form of the agricultural adjuvant pH buffer range from about pH4 to about pH 8 (at 20° C.):

Initial boiling point and boiling range >100° C. at 1 atmosphere

Flash point >100° C. at 1 atmosphere

Flammability (solid, gas) not relevant, (fluid)

Vapour pressure 0.013 Pa at 25° C.

Relative density 1-1.1 at 20° C. (water=1)

The agricultural adjuvant of this disclosure has been found to be stablein concentrated form or in diluted form. Further, when the agriculturaladjuvant is diluted and admixed with other agro-chemistries the tank mixremains stable without displaying unwanted side reaction such asprecipitation of chemicals. The flashpoint of over about 100° C. at 1atmosphere also shows an improvement in safety relative to the prior artshowcased herein. This also impacts the ease and cost of manufacture.

In use the agricultural adjuvant also provides for stability over abuffered range from about pH 4 to about pH 8 making its use in a tankmix with other chemistries versatile. In the examples herein below, theagricultural adjuvant when diluted in water in low concentrationsprovides several advantages over the prior art.

The at least one polyphenol containing natural or synthetic oilcomposition which is used as a component of the agricultural adjuvanthas not been found to be harmful to soil, plants or seed. This is incontrast to other natural oils such as orange oil and d-limonene whichare known to display phytotoxic effects at certain concentrations inuse.

Herein we show that the agricultural adjuvant of this disclosure ishighly effective to aid and facilitate biological and/or physiologicalactivity of active ingredients (such as a herbicide) but concomitantlydoes not have negative impacts on physico-chemical properties of activeingredients (such as a herbicide) present in a tank mix when in use.

In accordance with a fourth aspect of this disclosure there is provideduse of the agricultural adjuvant described in the first aspect of thisdisclosure in agriculture, said use comprising the steps of:

(i) combining the agricultural adjuvant of the first aspect togetherwith water and at least one agricultural compound selected from, but notlimited to, the group comprising: insecticides, fungicides, herbicides,desiccants, defoliants, acaricides, nutrients, miticides, bactericides,biocides, ovicides, nematicides, insect growth regulators, plant growthregulators, and combinations thereof, to provide a mixture; and

(ii) applying the mixture to plants, weeds, seeds, soil, urban places,and forests, via an apparatus selected from, but not limited to, thegroup comprising: air assisted sprayers, conventional sprayers,ultra-low volumes equipment such as aerial, electrostatic, foggers andmisting spray equipment and chemigation systems, pivots, sprinklers, andcombinations thereof.

In accordance with a fifth aspect of this disclosure there is providedan agricultural composition comprising:

at least one polyphenol containing natural or synthetic oil composition,which is preferably as described in the first to third aspects of thedisclosure above;

at least one anionic surfactant, which is preferably as described in thefirst to third aspects of the disclosure above;

at least one nonionic surfactant, which is preferably as described inthe first to third aspects of the disclosure above; and

at least one pH adjuster, which is preferably as described in the firstto third aspects of the disclosure above.

The agricultural composition of the fifth aspect of this disclosure mayfurther include at least one of, but not limited to, the followinggroup: insecticides, fungicides, herbicides, desiccants, defoliants,acaricides, nutrients, miticides, bactericides, biocides, ovicides,nematicides, insect growth regulators, plant growth regulators,fertilizers and combinations thereof.

The agricultural adjuvant of the fifth aspect of the invention mayfurther include an essential oil and may be kumquat (Citrus japonica)oil. Kumquat oil may comprise at least one of, but not limited to, thefollowing group: limonene (preferably d-limonene), alpha-pinene,bergamotene, caryophllene, α-humulene, α-muurolene, isopropylpropanoate, terpinyl acetate, carvone, citronellal, 2-methylundecanal,nerol and trans-linalool oxide.

The agricultural composition according to the fifth aspect of theinvention may be formulated and/or provided as a pesticide.

The agricultural composition may be for use in biocontrol applications,additionally or alternatively, as a biostimulant and/or a microbialstimulant. The agricultural composition may be safe for use withentomopathogenic nematodes (EPNs). The agricultural composition may beappropriate for post-harvest applications on crops and/or seeds.

The agricultural composition according to the fifth aspect of theinvention is typically formulated with additional chemistries and/or adiluent. The agricultural composition may provide a tank mix partnerproviding in use a stable tank mix. The agricultural composition mayprovide an in-can formulation partner providing in use a stable in-canformulation. Stability is an important property to ensure effective useand/or application of the agricultural formulation to plant, soil and/orseed material.

The agricultural composition when in use in a tank mix and/in in anin-can formulation provides increased stability and hindersprecipitation and/or gel formation. The agricultural composition furtherprovides that the tank mix and/or the in-can formulation remains stableover a pH range of from about 4 to about 8 providing for versatility inuse.

The agricultural composition may be provided as a tank mix and/or as anin-can formulation. Tank mixes may include multicomponentchemical-compositions mixed inside a tank from which irrigation and/orfertigation will take place. In-can formulations include multicomponentchemical-compositions within a single can (or container), whereinindividual components may have different chemical properties when in useand wherein the single can (or container) may be sold as a standaloneitem including therein the different multi-components.

Without being limited to theory, the Applicant believes that thepolyphenols of the present disclosure impart surprising and unexpectedimprovements in the physico-chemical properties over the prior art. Itis the unique interaction between the various components that comprisethe disclosure including the polyphenols that unexpectedly provide theadvantages. There is no suggestion, motivation or hint in the prior artthat would lead the skilled person to provide for the disclosure asherein described. The Applicant submits that arriving at its disclosureherein by relying on non suggestive prior art would require aninordinately voluminous amount of undue experimentation.

Non-Limiting Examples

Non-limiting examples of the disclosure are provided here below. Anagricultural adjuvant and/or agricultural composition according to theabove aspects of the disclosure were prepared according to the Tables 1to 5 below by way of example only.

The disclosures below are not to be construed as limiting. It is to beunderstood that the wt. % is a total for the formulation/compositionprepared.

TABLE 1 Example embodiments of the disclosure More Most Preferredpreferred preferred range range range Chemical component % w/w % w/w %w/w polyphenol containing 1 to 40 1 to 20 2 to 10 natural or syntheticoil composition anionic surfactant 2 to 65 2 to 60 10 to 50 nonionicsurfactant 2 to 25 2 to 20 5 to 10 pH adjuster 1 to 15 1 to 10 1 to 5diluent (water) 20 to 85 40 to 60 50 to 60

TABLE 2 Further example embodiments of the disclosure More MostPreferred preferred preferred range range range Chemical component % w/w% w/w % w/w Diluent (example: water) 30 to 70 40 to 60 50 to 60 pHadjuster (example: sodium 0.5 to 10 0.5 to 3 1 to 3 hydroxide) anionicsurfactant (example 0.5 to 30 0.5 to 15 5 to 10 dodecyl benzene sulfonicacid) anionic surfactant (example: 5 to 40 10 to 20 15 to 20 sodiumlaurel ether sulphate) non-ionic surfactant (example: 3 to 15 5 to 20 5to 10 primary or secondary alcohol C11-15 ethoxylates) anionicsurfactant (example: 0.5 to 10 0.5 to 5 1 to 3 alkenes, C14-16 alpha,sulfonate) polyphenol containing natural 1 to 40 2 to 20 2 to 10 orsynthetic oil composition (example: Ribes Nigrum (Black currant) seedoil pH adjuster (example: citric 0.5 to 10 0.5 to 5 1 to 3 acid)

TABLE 3 Further example embodiments of the disclosure More MostPreferred preferred preferred range range range Chemical component % w/w% w/w % w/w Diluent (example: water) 30 to 70 40 to 60 50 to 60 pHadjuster (example: sodium 0.5 to 10 0.5 to 3 1 to 3 hydroxide) anionicsurfactant (example 0.5 to 30 0.5 to 15 5 to 10 dodecyl benzene sulfonicacid) anionic surfactant (example: 5 to 40 10 to 20 15 to 20 sodiumlaurel ether sulphate) non-ionic surfactant (example: 3 to 15 5 to 20 5to 10 primary or secondary alcohol C11-15 ethoxylates) anionicsurfactant (example: 0.5 to 10 0.5 to 5 1 to 3 alkenes, C14-16 alpha,sulfonate) polyphenol containing natural or 1 to 40 2 to 20 2 to 10synthetic oil composition (example: Ribes Nigrum (Black currant) seedoil Essential oil (example: Citrus 0.05 to 5 0.5 to 3 0.8 to 2 japonicaoil) pH adjuster (example: citric acid) 0.5 to 10 0.5 to 5 1 to 3

TABLE 4 Further example embodiments of the disclosure More MostPreferred preferred preferred range range range Chemical component % w/w% w/w % w/w Diluent (example: water) 30 to 70 40 to 60 50 to 60 pHadjuster (example: sodium 0.5 to 10 0.5 to 3 1 to 3 hydroxide) anionicsurfactant (example 0.5 to 30 0.5 to 15 5 to 10 dodecyl benzene sulfonicacid) anionic surfactant (example: 5 to 40 10 to 20 15 to 20 sodiumlaurel ether sulphate) non-ionic surfactant (example: 3 to 15 5 to 20 5to 10 primary or secondary alcohol C11-15 ethoxylates) anionicsurfactant (example: 0.5 to 10 0.5 to 5 1 to 3 alkenes, C14-16 alpha,sulfonate) polyphenols (example: Ribes 1 to 40 2 to 20 2 to 10 Nigrum(Black currant) seed oil Essential oil (example: Citrus 0.05 to 5 0.5 to3 0.8 to 2 japonica oil) pH adjuster (example: citric 0.5 to 10 0.5 to 51 to 3 acid) Antioxidant (butyl hydroxy 0.05 to 5 0.05 to 2 0.1 to 0.5toluene) Preservatives (example: 1,2 0.1 to 5 0.3 to 3 0.4 to 1.5benzisothiazolin-3-one and/or 2-Phenoxy ethanol) Stabiliser (example:urea) 0.1 to 5 0.1 to 2 0.5 to 1.5

TABLE 5 Further example embodiments of the disclosure More MostPreferred preferred preferred range range range Chemical component % w/w% w/w % w/w Diluent (example: water) 30 to 70 40 to 60 50 to 60 pHadjuster (example: sodium 0.5 to 10 0.5 to 3 1 to 3 hydroxide) anionicsurfactant (example 0.5 to 30 0.5 to 15 5 to 10 dodecyl benzene sulfonicacid) anionic surfactant (example: 5 to 40 10 to 20 15 to 20 sodiumlaurel ether sulphate) non-ionic surfactant (example: 3 to 15 5 to 20 5to 10 primary or secondary alcohol C11-15 ethoxylates) anionicsurfactant (example: 0.5 to 10 0.5 to 5 1 to 3 alkenes, C14-16 alpha,sulfonate) polyphenols (example: Ribes 1 to 40 2 to 20 2 to 10 Nigrum(Black currant) seed oil pH adjuster (example: citric 0.5 to 10 0.5 to 51 to 3 acid) Antioxidant (example: butyl 0.05 to 5 0.05 to 2 0.1 to 0.5hydroxy toluene) Preservatives (example: 1,2 0.1 to 5 0.3 to 3 0.4 to1.5 benzisothiazolin-3-one and/or 2-Phenoxy ethanol) Stabiliser(example: urea) 0.1 to 5 0.1 to 2 0.5 to 1.5

All the embodiments of the disclosure in Tables 1 to 5 were stableliquids in the concentrated form. The concentrated forms were suitablefor dilution to prepare diluted forms as described herein.

Conventionally, research on agricultural adjuvants was mainly based onempirical and heuristic studies with a central goal of maximisingdelivery of active ingredient. Consideration as to basic principlesregarding a mode of action (MoA) was typically disregarded.

Practically, when providing agricultural adjuvants the following factorsrequire investigation:

-   -   1) droplet formation of the adjuvant during flight from a nozzle        of an irrigation or fertigation means to a target surface on a        leaf of a plant;    -   2) contact (imping) of the adjuvant droplet on the leaf which        results either in the adjuvant droplet being retained, or        bouncing off of the leaf, or in the adjuvant drop shattering.    -   3) wetting or spreading process of the adjuvant on the leaf        surface.    -   4) what happens on the leaf surface—properties of the adjuvant        deposit?    -   5) penetration of the adjuvant through plant cuticular membrane        (which is the first barrier for organic molecules to pass).

The physico-chemical nature of agricultural adjuvants may have a stronginfluence on individual factors (1) to (5) above, or on several factorsconcomitantly. Further, it can be seen that only are thephysico-chemical properties of the adjuvant concentrate important, butalso when diluted in water and applied in use to a leaf of a plant. Theagricultural adjuvant of the first aspect of this disclosure inconcentrate form provides for a stable, homogenous liquid. When dilutedthe agricultural adjuvant of this disclosure remains a stable emulsionor micro-emulsion and is buffered over a pH range.

The agricultural adjuvant according to the first aspect of thisdisclosure is investigated against an available commercial adjuvantregarding the above factors below.

Adjuvant Droplet Formation, Retention and Wetting

The agricultural adjuvant in concentrate form is diluted in accordancewith the third aspect herein above.

In an example, preparation of the aqueous spray liquid solutionincluding the agricultural adjuvant of this disclosure is provided in atank of a boom sprayer. In use, a spray nozzle of the boom sprayeratomises the liquid diluted agricultural adjuvant into small droplets(having a typical mean volume of 200 μm³) which are formed during thefirst milliseconds of the flight as the adjuvant droplet exits thenozzle. As the impact on the leaf surface occurs typically after 50 to400 ms after exit from the nozzle, the time frame during the adjuvantdroplet trajectory is a sensitive high-speed process. Either the dropletsuccessfully reaches the target plant and then spreads on its surface orbounces off and will be lost to the ground. The third possibility isthat the droplet shatters or splashes on the solid plant surface. Adroplet is said to shatter whenever it disintegrates into two or moresecondary droplets, including the separation into tiny droplets aftercolliding.

Accordingly, adhesion or retention of an adjuvant droplet on the targetsurface on the plant is a key prerequisite for a successful applicationof plant protection agents, especially for super-hydrophilic plantsurfaces which are difficult to wet because of diverse surfacestructures like hairs, epicuticular wax crystals or others. Plants withsmooth wax surfaces are easy to wet, so spray droplet retention is lessof a concern since a water droplet alone will adhere. Certainly, thefirst milliseconds of the application process are sensitively affectedby a number of variables.

The characterisation of the wettability and the hydrophobicity of thesurface of the plant must be determined with the water contact anglemeasurement.

The agricultural adjuvant of this disclosure includes at least oneanionic and at least one non-ionic surfactant. Anionic and non-ionicsurfactants have an impact on surface tension. The dynamic surfacetension (DST) differs from the equilibrium value (STeq). Small amountsof anionic and/or non-ionic surfactants can cause alterations of thesurface tension of the diluted adjuvant droplet. The reason for this isthat the interface between the aqueous adjuvant droplet (includingsurfactant) and the surrounding gaseous phase, which is producedextremely quickly. Therefore, the kinetics of the interface formationneeds to be kept in mind. The mobility of surfactant molecules becomesan important factor in the formation of the dynamic surface tension. Theinteractions between the anionic and nonionic surfactants and the atleast one polyphenol containing natural or synthetic oil composition arealso important. The non-covalent bonding, ionic bonding, electrostaticinteractions, hydrogen bonding, and van der Waals forces between theessential features of the agricultural composition of this disclosure(both in concentrate and/or dilute forms) facilitate providing thedesirable physico-chemical properties in use. Surprisingly theagricultural adjuvant of this disclosure showed little foaming andwithout being limited to theory this is thought to be a function of theunique and unpredictable interaction between the various essentialchemical components of the agricultural adjuvant.

The ideal consequence of contact of dilute adjuvant droplets on the leafsurface is the adjuvant droplet adherence to the leaf surface. But itcan also result either in bouncing off or in drop shattering. Aftersuccessful retention, the adjuvant droplet begins to spread on the leaf.The reduction of interfacial tension is one of the most crucialphysico-chemical properties of surfactants, which influence dropletretention and spreading characteristics on plants.

The surface tension of the prior art WETCIT® (a commercially availableadjuvant including on a natural orange oil terpene) and theadjuvant/agricultural composition of this disclosure (ORO-368) wasmonitored to characterise the surface tension lowering behaviour, whichis due to the velocity of individual droplets. When individual dropletsare fully saturated on the droplet interface, a static or equilibriumsurface tension value can be determined. This value was measured by aring method considering processes, like spreading or run-off effects.The test example ORO-368 was made as per Table 3 and particularly withinthe most preferred ranges provided therein.

Materials and Methods Surface Tension

The surface tension of different dilutions of aqueous solutions ofWETCIT and the agricultural adjuvant of this disclosure (ORO-368) wereinvestigated with the help of a Krüss Digital Tensiometer K10 (KrüssGmbH, Hamburg, Germany) using the ‘Du Noüy’ ring method. At least 10replicates of each sample were measured per substance solution and amean value was calculated. Between each measurement, the solution wasleft for at least 5 minutes to allow equilibration between vapor andliquid.

Contact Angle Measurement

Surface material Parafilm was used as an artificial, apolar controlsurface having no surface structures. A winter wheat cultivar Triticumaestivum was used as a model plant during growth stage BBCH 12(2-leaf-stadium). The second leaf was sampled for contact anglemeasurements. Specimen slides were prepared with double-sided adhesivetape. Plant material was carefully placed on specimen slides. All plantmaterial was transported and stored in a box with a wet paper towel toprevent fast transpiration. Contact angle measurements were performedwith an optical contact angle measuring device OCA 20 (DataPhysicsInstruments GmbH, Filderstadt, Germany) A 3 μL droplet was placed on theleaf surface by touching. At least 10 droplet replicates were measuredper substance and surface. The contact angle was determined from theshadow image of the sessile droplet and analysed with the drop shapeanalysis (DSA) software. A contour recognition was initially carried outbased on a grey-scale analysis of the image. In the second step, ageometrical model describing the drop shape is fitted to the contour(Krüss GmbH. Drop shape analysis). The contact angle is considered bythe angle between the calculated drop shape function and the samplesurface.

Droplet Spread Area

After complete evaporation of water from the droplets used for contactangle measurements, areas of dry spray deposits were further analysedusing a microscope, Zeiss Scope A1 which was equipped with a camera(AxioCam MRc, Carl Zeiss Microscopy GmbH). A red dye was used as amarker for visualisation of the borders of the droplet residue. Thedetermination of the droplet spread area was carried out with thesoftware AxioVision Rd. 4.8 (Carl Zeiss Microscopy GmbH).

Visualisation of Surface Structures by SEM

Micromorphological investigations of surface structures and agriculturaladjuvant residues on fresh leaf material were performed with a scanningelectron microscopy (JEOL JSM-7500F, JEOL GmbH, Freising, Germany)equipped with a field emission gun and LEI and SEI detectors. Fresh leafmaterial of Triticum aestivum was used for SEM experiments. Plants wereused in growth stage BBCH 12. To illustrate contact areas between theleaf surface and the surfactant solution, 0.1% WETCIT® and theagricultural adjuvant of this disclosure (ORO 368) surfactant solutiondroplets (0.2 μL) were carefully applied on the surface. Fresh plantmaterial with droplet deposits was mounted on aluminium holders,carefully air dried on silica gel, then sputter-coated with ˜3 nmplatinum. For the visualisation of surfactant deposits, the LEI detectorwas used, as well as the SEI detector.

Results Equilibrium Surface Tension

The surface tension of both adjuvants, WETCIT® and the agriculturaladjuvant of this disclosure (ORO 368) diluted in water (w/v) atdifferent dilution rates was determined by the ring method (Table 6).Pure water (dest.) was used as a control. At room temperature (20° C.),the surface tension value for water was defined at 72.75 mN m⁻¹. The ORO368 shows a lower surface tension and lower contact angles providing fora superior adjuvant when compared to the commercially available WETCIT®.It is the unique combination of essential features of the agriculturaladjuvant that allows these physico-chemical properties in use whendiluted in water.

TABLE 6 Results of the equilibrium surface tension (STeq) using the ringmethod and the contact angle measured 60 s after droplet settling of thediluted samples of WETCIT and ORO 368. Percent Dilution SAMPLE 0.50%0.20% 0.10% 0.05% 0.01% Product Equilibrium Surface Tension (mN/n)WETCIT 31.6 31.6 31.9 31.9 31.7 OR-368 28 28 28.6 28.2 28.3 ProductContact Angle (°) WETCIT 41.95 46.45 45.9 42.45 45 OR-368 30.1 30.5 31.634.65 38.25

Contact Angle Measurement

The determination of time-dependent sessile contact angles (CA) wascarried out to characterise the surfactant wetting and spreadingpotential on the one hand, but also to investigate surface properties ofa plant surface of wheat leaves on the other hand. The process ofdroplet spreading after 2 seconds, 30 s and finally 60 s after dropletsettling was studied. Parafilm was used as an artificial control surfaceconsidering differences between selected surfactant samples. In Table 1are shown the average results of the 60 s data. In table 2 the analysisover the 2, 30 and 60 s period. All samples were dissolved in water atdifferent dilutions. A red dye (0.1%, w/v) was added to all surfactantsolutions for further visualisation of the droplet residue after waterevaporation. Pure water (distilled) was adopted as control experiment.During the complete time interval of 60 s water contact angle remainedconstant at a value of about 107°. Between the surfactants, a slightdifference became visible (Table 7). WETCIT® Cas values were around 55°which decreased during the first minute. ORO 368 showed the highestdecrease in CA during the first minute after droplet application andlower, compared to the pure water. Moreover, all the contact anglesdecreased steeply during the first 30 s.

TABLE 7 Mean of the contact angle [°] of the water diluted formulationsof WETCIT  ® and ORO 368 after 2, 30 and 60 s after droplet settlingContact angle Contact angle Contact angle Sample [°] after 2 s [°] after30 s [°]after 60 s WETCIT 0.5% 52.35 45.6 41.95 WETCIT 0.2% 57.90 49.346.45 WETCIT 0.1% 52.1 47.4 45.9 WETCIT 0.05% 51.2 46.3 42.45 WETCIT0.01% 54.7 49.1 45 ORO-368 0.5% 43.2 37.3 30.1 ORO-368 0.2% 42.9 36.730.5 ORO-368 0.1% 43.0 38.2 31.6 ORO-368 0.05% 45.9 40.1 34.65 ORO-3680.01% 47.6 42.2 38.25

The determination of time-dependent sessile CAs was also carried out tocharacterise the wetting capability of surfactants considering the plantsurface of Triticum aestivum. Therefore, CAs of WETCT® dilution rate0.1% and ORO 368 on the dilution rates 0.1% and 0.05% on both, theadaxial (FIG. 1 ) and the abaxial side (FIG. 2 ) were analysed. Purewater (dest.) was used again as control experiment. On the upper side ofthe leaf, water CAs remained constant at a high value of about 125°during the one minute (FIG. 1 ). All surfactants had the ability tolower the CA compared to water, even on a low level. While WETCIT 0.1%produced a final CA of 90°, ORO 368 0.1% had the minimum CA of 68° inthis experiment. Also the shape of the CA development was steepest forORO 368 0.1%.

The water CA on the abaxial side of the leaf was slightly lower than onthe upper side (lower side: 145°, upper side: 115°) (FIG. 2 ).Furthermore, CA results of all the samples were slightly smaller thanthe upper side experiment but had generally the same characteristics.

The minimum CAs was observed for ORO 368 0.1%, around 38° after 60 s.Compared to the results generated on parafilm, the ability of surfactantsolutions to decrease the CA on the surface of wheat was lower duringthe first seconds of measurement.

Droplet Spread Area

After the complete evaporation of water from the 3 μL droplets, measuredin contact angle experiments, the remaining dry and red deposits fromthe strawberry-red azo dye Sanolin Ponceau (which was added to allsurfactant solutions (0.1%, w/v)) were used for further visualisation ofthe droplet spread area on adaxial and abaxial leaf surfaces of Triticumaestivum by microscope (FIG. 4 ). The different drying times of dropletswere not recorded.

Water droplets were used here as a control and resulted in a minimumcovered leaf area (0.6 mm²±0.3) (FIG. 3 and FIG. 4 ). In comparison towater, all surfactant solutions had an increasing effect on the coveredleaf area, although differences between the adaxial and abaxial side ofthe wheat leaf were not visible.

The maximum covered leaf area was measured for ORO 368 (0.1%) (upperside: 9.6 mm²; lower side: 6.4 mm²) (FIG. 4 ). WETCIT (0.1%), had a leafarea ranging from 6.2 to 5.6 mm².

Visualisation of Surface Structures by SEM

Investigations of surface analysis by scanning electron microscopy (SEM)should visualise microstructures of plant surfaces and might displaydifferences between the surfactant samples used for wetting experiments.

Parafilm was used as a synthetic surface for contact angle measurements,considering basic differences between surfactant samples. Parafilm isknown to be strong apolar and free of any surface structures. The SEMpicture showed no or only very small surface imperfections (FIG. 5 ).

Differences between both sides of Triticum aestivum leaves wereobservable in a low magnification (50×, FIGS. 6 , A and B).Non-glandular trichomes were orientated in parallel on both sides. Theupper side hairs are longer than the lower side ones (not measured).However, the hair density of around 10 trichomes per mm² is half as muchcompared to the abaxial side, having around 20 hairs per mm². Thesurface of trichomes on both sides is free of any epicuticular waxcrystals (FIGS. 6 , C and D). Though, epicuticular wax crystals are thepredominant microstructural element on the wheat surface on both sidesof the leaf (FIGS. 6 , E and F). The density of wax crystals seems to beslightly higher on the adaxial side, because of more free ‘gaps’ in thewax crystal coverage on the abaxial side.

Leaf material of Triticum aestivum was also used to show differencesbetween the samples by applying small droplets on the adaxial surface.The residue was not washed or cleaned after application, because the drysurfactant deposit was studied. Therefore, the borders between thedroplet and the non-treated areas were visualised. The influence oftrichomes was not investigated in these experiments. SEM pictures wereselected to display a representative result of several observedimpressions.

The application of both WETCIT® and ORO 368 at 0.1% caused a formationof a smooth, amorphous deposit which covered the surface including theepicuticular wax crystals. The peaks of wax crystals stick out of thedeposit layer. The borderline is clearly visible in the center of bothimages (FIG. 7 ). With WETCIT® the border between the droplet and thetreated area was clearly visible as a sharp line. At the borderline ofthe crusted layer, a lifting or detaching could be observed by a shadow(FIGS. 7 , B and D).

Additional contact angle measurements were taken comparing thedisclosure ORO 368 against prior art adjuvants. The contact angle forthe water used was 94°. The contact angle for water plus commercial cropoil concentrate (COC) was 58°. The contact angle for water pluscommercial modified seed oil (MSO) was 59°. The contact angle for waterplus commercial non-ionic surfactant (NIS) was 38°. And finally thecontact angle for water plus ORO 368 was 29°. This shows a significantimprovement over standard prior art adjuvants. Further, spreading anddeposition properties were evaluated. FIG. 8 shows the superiorspreading and deposition properties of ORO 368 against prior artstandard adjuvants. A hallmark of an effective agricultural adjuvantincludes its ability to facilitate spreading over a surface. FIG. 8 wasgenerated by applying ORO 368 and the prior art adjuvants to paper.

Field Trials

Efficacy and crop selectivity of ORO 368 were conducted in a tank mixagainst Septoria tritici in wheat. A standard fungicide was used calledAMPERA to evaluate the efficacy of ORO 368 as an adjuvant. AMPERAincludes prochloraz and tebuconazole as active ingredients. Theexperiment protocol is shown below and the results are shown in FIG. 9 .FIG. 9 (A) shows AMPERA alone, (B) shows AMPERA plus ORO 368 at 0.25%,(C) shows AMPERA plus ORO 368 at 0.5%, and (D) shows AMPERA plus priorart WETCIT® at 0.25%. From FIG. 9 it can clearly be seen that ORO 368shows improvements over the prior art, and functions well to bolster theeffect of an active ingredient. The results of FIG. 9 are seven (7) daysafter application.

TABLE 8 Trial protocol for efficacy and crop selectivity of ORO 368against Septoria tritici in wheat. Treatment Concen- no. Type Nametration Type Rate 1 Control/ Untreated 400 g/L EC 1.5 litres Untreatedcontrol (emulsifiable per hectare concentrate) 2 Fungicide AMPERA 400g/L EC 1.5 litres per hectare 3 Fungicide AMPERA 400 g/L EC 1.5 litresplus per hectare ORO-368 adjuvant 4 Fungicide AMPERA 400 g/L EC 1.5litres plus per hectare ORO-368 adjuvant 5 Fungicide AMPERA 400 g/L EC1.5 litres plus per hectare ORO-368 adjuvant Replications 4. Untreatedtreatments 1. Conduct under GLP/GEP: YES. Design: randomized completeblock. Treatment units: Treated plot experimental unit size width 4meters, length 6 meters. Application volume 200 L/ha.

FIGS. 10 and 11 shows efficacy evaluation of ORO 368 with a herbicidesold as HARMONY SX in maize thirteen (13) [*] and twenty-one (21) [**]days after application. HARMONY SX includes thifensulfron as activeingredient.

TABLE 8 Trial protocol for efficacy evaluation of ORO 368 with anherbicide sold as HARMONY SX in maize. Treatment Concen- no. Type Nametration Type Rate 1 Control 15 g/hectare Tank mix 7.5 g emulsion ai/ha 2Herbicide HARMONY 15 g/hectare Tank mix 7.5 g emulsion ai/ha 3 HerbicideHARMONY 15 g/hectare Tank mix 7.5 g and ORO plus ORO emulsion ai/ha 368368 4 Herbicide HARMONY 15 g/hectare Tank mix 7.5 g plus plus emulsionai/ha WETCIT ® WETCIT Replications 4. Untreated treatments 1. Conductunder GLP/GEP: YES. Design: randomized complete block. Treatment units:Treated plot experimental unit size width 4 meters, length 6 meters.Application volume 200 L/ha.

FIGS. 10 and 11 show the efficacy of against a range of pests in maize100% efficacy indicates the elimination of the weed or unwanted plant.It is shown that the adjuvant of ORO 368 (also WETCIT NEO in FIGS. 10and 11 ) is in fact effective in bolstering the effect of the herbicide.

Conclusions: Surface Tension Measurements

Surface tension experiments were performed to analyse the surfactantsolutions considering their ability to lower the physical value ofsurface tension during a critical time frame. During foliar applicationin the field, the majority of spray droplets impact the leaf surfaceafter about 50 to 400 ms.

During the complete time interval, no decrease of surface tension ofpure water could be observed and the ST remained constant at a value ofabout 72 mN m−1 which is defined as literature surface tension value forpure water at 20° C. This result confirms that there are no surfaceactive contaminations in the water which serves as the solvent mediumfor all other surfactant solutions. The high surface tension value ofpure water reflects the high intermolecular attractions of watermolecules. As the surface tension of water is a function of temperature,the literature value of water (72.75 mN m−1 at 20° C.) is closelycomparable to the results shown herein. The influence of the waterhardness on the surface tension is negligible.

All experiments were conducted using different surfactant concentrationsfor WETCIT® and ORO-368 in water. These concentrations were selectedbecause it is in-between the typical range of commonly used WETCT®concentrations for agricultural spray formulations and more importantly,this value is high above the critical micelle concentration (cmc).Therefore, the formation of micellar aggregates in the bulk phase of thewater solvent is ensured. With this, the complete saturation of thewater-air interface with surfactant individual droplets (microscopicdrop of the formulation) is guaranteed and an equilibrium state can bereached constantly.

All the dilutions of the surfactant samples were able to decrease thesurface tension to the critical value of about 55 to 60 mN m⁻¹.

The lowest measured value was 28 mN m⁻¹ for ORO 368 demonstrates surfacetension lowering properties that will improve retention effects forspraying superhydrophobic plant surfaces.

Wetting Characteristics of Selected Surfactants

The term ‘wetting agent’ is applied to any substance that increases theability of water or an aqueous solution to displace air from a solidsurface. This surface property is shown by all surface-active agents,although the extent to which they exhibit this phenomenon variesgreatly. The water contact angle (CA) test is generally applied as asimple and easy to measure method of evaluating the wettability ofdifferent plant species. Therefore, the CA is a unit for the wettabilityof surfaces. A low water CA of <10°-0° is indicative of asuperhydrophilic surface, CAs <90° would characterise surfaces that arehydrophilic or easy to wet. Results up between 90 and 150° are regardedas difficult-to-wet or hydrophobic and CAs over 150° are extremelydifficult-to-wet or superhydrophobic surfaces.

As the water CA on parafilm had a relatively high value (107°), thesurface must be assessed to be apolar. On the plant surface of Triticumaestivum, the adaxial and abaxial leaf surface was distinguished. Theadaxial side had a higher CA (145°), than the abaxial side (115°). Bothvalues are very high and indicate a very hard to wet surface, whereasthe adaxial surface has to be classified as superhydrophobic.

In the literature, there are some critical debates about the best way tocharacterise wettability of difficult-to-wet species, like Poaceae.Resulting water CAs are often immeasurably high to be able to rank thesespecies for wettability. It has been recommended that the use of a 20%acetone in water solution (v/v) as a test solution to characterise theseplant surfaces.

The observation of plant surfaces having hydrophobic characteristics isbased on the lipophilic wax surface of the plant cuticle. Investigationsof the chemical wax composition of Triticum aestivum coincided withliterature data and revealed a main component class of primary alcoholswith the predominant octacosanol (C₂₈ alcohol) (>70%). Scanning electronmicroscopy (SEM) analyses also showed hierarchical organisedmicro-structures like convex epidermal cells (not shown) withepicuticular wax crystals sitting on their surface (FIG. 6 ). Moreover,both leaf sides of wheat showed a high number of non-glandulartrichomes, whereas the density on the adaxial side was half as much thanon the abaxial side. In general, trichomes have a strong influence onleaf wettability. It has been shown that leaves with trichomes were morewater repellent, especially where trichrome density was greater than 25mm². But it has also been observed that some hairy species are able toentrap droplets with their trichomes. Further it has been reported thatwetting of plants covered with hairs strongly depends on the presence orabsence of epicuticular wax crystals on their surface. Leaves coveredwith non-waxy hairs were only water repellent for a short time after awater droplet had been applied. In contrast, leaves with waxy trichomeswere extremely water repellent, although the trichomes were up to 2 mmhigh and only loosely distributed over the leaf surface. The resultsfound for Triticum aestivum support this theory. The abaxial side showedtwice as much non-waxy hairs and resulted in lower CAs in general,compared to the adaxial side covered by less trichomes. The trichomesmight be evaluated as ‘hydrophilic peaks’ sitting on an extremelyhydrophobic surface.

The optical estimation of SEM samples revealed that the wax crystaldensity was slightly higher on the adaxial side, because of more free‘gaps’ in the wax crystal coverage on the abaxial side. This findingalso supports the conclusion of the abaxial side having better wettingcharacteristics than the adaxial side, although it is only slightlybetter.

As already mentioned, the CA analysis can be generally applied as asimple and easy to measure method.

Herein, the hysteresis angle is regarded as a sessile droplet which wasobserved to spread over a surface during a certain time period. Thechange of the CA of this sessile droplet was therefore recorded with acamera. Since evaporation of water should be avoided during CA analysis,the droplet volume was set at 3 μL and the measurement was persisted formaximal one minute. The information about CA change might give evidenceabout spreading properties of surfactants. In this study, all thesurfactant droplets decreased the CA during the first 5 to 10 seconds onparafilm. After about 10 seconds spreading was finished and a CA declinewas no longer observed. However, the initial CA was reduced compared tothe water CA which did not change over time.

The further spreading which lasted much longer than one minute wasanalysed by the droplet spread area after the evaporation of water. Thediameter of the residue of the added red dye was measured by microscope.The covered leaf area was higher for ORO 368 0.1% on the adaxial side,than for WETCIT® same dilution rate. From the CA results, one wouldsuggest the abaxial side to be better to wet than the adaxial sidebecause of already discussed reasons. Contrastingly, results of dropletspread area showed slightly lower values for the abaxial side, butdifferences may not be statistically significant.

The Applicant submits that the disclosure herein amelioratesdisadvantages known from the prior art.

1. An agricultural adjuvant comprising: black currant (Ribes nigrum)seed oil; at least one anionic surfactant selected from the groupconsisting of (C₆-C₁₈) alkyl benzene sulfonic acid, calciumdodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, amine(C₆-C₁₈) alkyl benzene sulfonate, and triethanolamine dodecylbenzenesulfonates; at least one nonionic surfactant selected from the groupconsisting of a natural and/or synthetic (C₈-C₂₂) alkoxylated fattyalcohols, (C₈-C₂₂) ethoxylated fatty alcohols, (C₈-C₂₂), propoxylatedfatty alcohols, (C₈-C₂₂), ethoxylated and propoxylated fatty alcohols,straight chain (C₄-C₁₀) alkyl(poly)glycosides, branched chain (C₄-C₁₀)alkyl(poly)glycosides; and alkoxylated sorbitan fatty esters,alkoxylated sorbitol fatty esters, ethoxylated sorbitan fatty esters,ethoxylated sorbitol fatty esters, polyoxyethylene sorbitan monolaurate,polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitanmonostearate, and combinations thereof; at least one pH adjuster; andwater from 51 to about 80 wt. %.
 2. The agricultural adjuvant of claim1, wherein the black currant (Ribes nigrum) seed oil comprises at leasttwo selected from the group consisting of delphinidin-3-rutinoside,delphinidin-3-glucoside, cyanidin-3-rutinoside, cyanidin-3-glucoside,myricetin-3-rutinoside, myricetin-3-glucoside, quercetin-3-rutinoside,quercetin-3-glucoside, kaempferol-3-glucoside, dihydroquercetin,aureusidin, 1-p-coumaroyl-β-d-glucopyranoside,1-cinnamoyl-β-d-glucopyranoside, caffeic acid, ferulic acid, p-coumaricacid, gallic acid, protocatechuic acid and p-hydroxybenzoic acid.
 3. Theagricultural adjuvant of claim 2, wherein the at least one polyphenolcontaining natural or synthetic oil composition further includes anatural oil composition of vegetable origin and is from a gymnosperm,preferably the gymnosperm.
 4. The agricultural adjuvant of claim 1,further comprising at least one anionic surfactant selected from thegroup consisting of (C₆-C₁₈) alkyl ether sulfates, (C₆-C₁₈) alkylethoxylated ether sulfates, (C₆-C₁₈) alkyl sulfates, lauryl etherpolyethoxylated sodium sulfate, (C₆-C₁₈) alkyl phosphate esters,(C₆-C₁₈) alkoxylated sulfates, (C₆-C₁₈) alkoxylated phosphate esters,xylene sulfonate salts, cumene sulfonate salts, and combinationsthereof.
 5. The agricultural adjuvant of claim 4, wherein the at leastone anionic surfactant comprises dodecylbenzene sulfonic acid and sodiumlaurel ether sulphate (SLES).
 6. The agricultural adjuvant of claim 1,wherein the non-ionic surfactant comprises secondary alcohol (C₁₁-C₁₅)ethoxylates.
 7. The agricultural adjuvant of claim 1, wherein the pHadjuster include a basic and/or an acidic compound.
 8. The agriculturaladjuvant of claim 7, wherein the pH adjuster includes sodium hydroxideand/or citric acid monohydrate.
 9. The agricultural adjuvant of claim 1,further comprising kumquat (Citrus japonica) oil wherein the kumquat oilcomprises at least two selected from the group consisting of limonene(preferably d-limonene), alpha-pinene, bergamotene caryophllene,α-humulene, α-muurolene, isopropyl propanoate, terpinyl acetate,carvone, citronellal, 2-methylundecanal, nerol and trans-linalool oxide.10. The agricultural adjuvant of claim 1, further comprising an additiveselected from the group consisting of preservatives, clarifiers,anti-freezing agents, hydrotropes, stabilizers, antioxidants,acidifiers, chelates, complexing agents, dyes, rheology modifiers,antifoams, anti-drift and solvents, and combinations thereof.
 11. Theagricultural adjuvant of claim 1 wherein: the black currant (Ribesnigrum) seed oil present in an amount of between 1 wt. % to 20 wt. %;the at least one anionic surfactant present in an amount of between 2wt. % to 60 wt. %; the at least one nonionic surfactant present in anamount of between 2 wt. % to 20 wt. %; and the at least one pH adjusterpresent in an amount of between 1 wt. % to 10 wt. %, wherein the wt. %is a total for the adjuvant; and wherein the at least one anionicsurfactant includes dodecylbenzene sulfonic acid and sodium laurel ethersulphate (SLES); and wherein the at least one nonionic surfactantincludes secondary alcohol (C₁₁-C₁₅) ethoxylates; and wherein the pHadjuster includes sodium hydroxide and/or citric acid monohydrate. 12.An agricultural composition comprising: black currant (Ribes nigrum)seed oil; at least one anionic surfactant selected from the groupconsisting of: (C₆-C₁₈) alkyl benzene sulfonic acid, calciumdodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, amine(C₆-C₁₈) alkyl benzene sulfonate, and triethanolamine dodecylbenzenesulfonates; at least one nonionic surfactant selected from the groupconsisting of: natural and/or synthetic (C₈-C₂₂) alkoxylated fattyalcohols, (C₈-C₂₂) ethoxylated fatty alcohols, (C₈-C₂₂) propoxylatedfatty alcohols, (C₈-C₂₂) ethoxylated and propoxylated fatty alcohols,straight chain (C₄-C₁₀) alkyl(poly)glycosides, branched chain (C₄-C₁₀)alkyl(poly)glycosides; and alkoxylated sorbitan fatty esters,alkoxylated sorbitol fatty esters, ethoxylated sorbitan fatty esters,ethoxylated sorbitol fatty esters, polyoxyethylene sorbitan monolaurate,polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitanmonostearate, and combinations thereof; at least one pH adjuster; andwater from 51 to about 80 wt. %.
 13. The agricultural composition ofclaim 12, wherein the black currant (Ribes nigrum) seed oil comprises atleast two selected from the group consisting ofdelphinidin-3-rutinoside, delphinidin-3-glucoside,cyanidin-3-rutinoside, cyanidin-3-glucoside, myricetin-3-rutinoside,myricetin-3-glucoside, quercetin-3-rutinoside, quercetin-3-glucoside,kaempferol-3-glucoside, dihydroquercetin, aureusidin,1-p-coumaroyl-β-d-glucopyranoside, 1-cinnamoyl-β-d-glucopyranoside,caffeic acid, ferulic acid, p-coumaric acid, gallic acid, protocatechuicacid and p-hydroxybenzoic acid.
 14. The agricultural composition ofclaim 13, wherein the at least one polyphenol containing natural orsynthetic oil composition further includes a natural oil composition ofvegetable origin and is from a gymnosperm, preferably the gymnosperm.15. The agricultural composition of claim 12, further comprising atleast one anionic surfactant selected from the group consisting of:(C₆-C₁₈) alkyl ether sulfates, (C₆-C₁₈) alkyl ethoxylated ethersulfates, (C₆-C₁₈) alkyl sulfates, lauryl ether polyethoxylated sodiumsulfate, (C₆-C₁₈) alkyl phosphate esters, (C₆-C₁₈) alkoxylated sulfates,(C₆-C₁₈) alkoxylated phosphate esters, xylene sulfonate salts, cumenesulfonate salts, and combinations thereof.
 16. The agriculturalcomposition of claim 15, wherein the at least one anionic surfactantcomprises dodecylbenzene sulfonic acid and sodium laurel ether sulphate(SLES).
 17. The agricultural composition of claim 12, wherein thenon-ionic surfactant comprises secondary alcohol (C₁₁-C₁₅) ethoxylates.18. The agricultural composition of claim 12, wherein the pH adjusterinclude a basic and/or an acid compound, preferably the pH adjuster isat least one selected from the group consisting of: gluconic acid,barium carbonate, calcium chlorate, chlorous acid, sodium salt,hydrobromic acid, tricalcium citrate, and citric acid.
 19. Theagricultural composition of claim 18, wherein the pH adjuster includessodium hydroxide and/or citric acid monohydrate.
 20. The agriculturalcomposition of claim 12, further comprising kumquat (Citrus japonica)oil wherein the kumquat oil comprises at least two selected from thegroup consisting of: limonene (preferably d-limonene), alpha-pinene,bergamotene, caryophllene, α-humulene, α-muurolene, isopropylpropanoate, terpinyl acetate, carvone, citronellal, 2-methylundecanal,nerol and trans-linalool oxide.
 21. The agricultural composition ofclaim 12, wherein said composition provides a pesticidal agriculturalcomposition.
 22. The agricultural composition of claim 12, furthercomprising an additive selected from the group consisting of:preservatives, clarifiers, anti-freezing agents, hydrotropes,stabilizers, antioxidants, acidifiers, chelates, complexing agents,dyes, rheology modifiers, antifoams, anti-drift and solvents, andcombinations thereof.
 23. The agricultural composition of claim 12wherein: the black currant (Ribes nigrum) seed oil present in an amountof between 1 wt. % to 20 wt. %; the at least one anionic surfactantpresent in an amount of between 2 wt. % to 60 wt. %; the at least onenonionic surfactant present in an amount of between 2 wt. % to 20 wt. %;and the at least one pH adjuster present in an amount of between 1 wt. %to 10 wt. %, wherein the wt. % is a total for the adjuvant; and whereinthe at least one anionic surfactant includes dodecylbenzene sulfonicacid and sodium laurel ether sulphate (SLES); and wherein the at leastone nonionic surfactant includes secondary alcohol (C₁₁-C₁₅)ethoxylates; and wherein the pH adjuster includes sodium hydroxideand/or citric acid monohydrate.